Title: Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO 2 on Copper?

Abstract

It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO 2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 10 3 s –1. Oxygen can survive longer in deeper layers, but it does not promote CO 2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO 2 adsorption on copper.

@article{osti_1430685,
title = {Is Subsurface Oxygen Necessary for the Electrochemical Reduction of CO2 on Copper?},
author = {Garza, Alejandro J. and Bell, Alexis T. and Head-Gordon, Martin},
abstractNote = {It has recently been proposed that subsurface oxygen is crucial for the adsorption and subsequent electroreduction of CO2 on copper. Using density functional theory, we have studied the stability and diffusion of subsurface oxygen in single crystals of copper exposing (111) and (100) facets. Oxygen is at least 1.5 eV more stable on the surface than beneath it for both crystal orientations; interstitial sites are too small to accommodate oxygen. Here, the rate of atomic oxygen diffusion from one layer below a Cu(111) surface to the surface is 5 × 103 s–1. Oxygen can survive longer in deeper layers, but it does not promote CO2 adsorption there. Diffusion of subsurface oxygen is easier to the less-dense Cu(100) surface, even from lower layers (rate ≈ 1 × 107 s–1). Finally, once the applied voltage and dispersion forces are properly modeled, we find that subsurface oxygen is unnecessary for CO2 adsorption on copper.},
doi = {10.1021/acs.jpclett.7b03180},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 9,
place = {United States},
year = {2018},
month = {1}
}

The adsorption and oxidation of carbon monoxide were studied on model mono- and bimetallic catalysts of Pd(111), Pd(100), Cu(100), Rh(100) and Cu/Rh(100), using combined elevated pressure reactor/IR cell-UHV surface analysis systems. Adsorption studies were carried out in wide pressure and temperature ranges of 10[sup [minus]7]-10[sup 1] Torr and 90-1000 K, respectively, employing techniques of RAIRS and TPD. The adsorption of CO on Pd(111) was found to be very sensitive for the preparation conditions of the adsorbed CO layer. Isosteric heats of adsorption were determined for Pd(111) an equilibrium phase diagram was constructed which shows the continuity of CO molecules inmore » different adsorption positions. For Pd(111) an equilibrium phase diagram was constructed which shows the continuity of CO adsorption phases with increasing CO pressure and surface temperature. Excellent agreement was found between IR spectra of equilibrated CO layers on Pd(111) and Pd(100) single crystals and a Pd/SiO[sub 2] catalyst. Results of elevated pressure kinetic and IR measurements for the oxidation of CO on Pd(111) and Pd(100) strongly support the generally accepted correspondence between the heat of CO adsorption and the activation energy. Deposition of Cu on the Rh(100) surface results in an increase in catalytic activity for CO oxidation. Maximum activity is seen at [theta][sub Cu] = 1.3ML and the activity of Cu/Rh(100) catalysts are higher than that of Rh(100) even at [theta][sub Cu] > 3ML. The Cu overlayer is not stable under the oxidizing reaction conditions employed and by interacting with oxygen present in the reactant gas mixture it forms 3D Cu[sub x]O agglomerates. The kinetics of CO oxidation on Cu/Rh(100) catalysts are similar to those on Rh(100), the largest deviation is seen for catalysts with [theta][sub Cu] < 0.5ML. The role of Cu in the Cu/Rh(100) bimetallic catalysts is to increase the local oxygen concentration at the Cu-Rh peripheries.« less

High Pressure Scanning Tunneling Microscopy (HP-STM) and Ambient Pressure X-ray Photoelectron Spectroscopy were used to study the structural properties and catalytic behavior of noble metal surfaces at high pressure. HP-STM was used to study the structural rearrangement of the top most atomic surface layer of the metal surfaces in response to changes in gas pressure and reactive conditions. AP-XPS was applied to single crystal and nanoparticle systems to monitor changes in the chemical composition of the surface layer in response to changing gas conditions. STM studies on the Pt(100) crystal face showed the lifting of the Pt(100)-hex surface reconstruction inmore » the presence of CO, H 2, and Benzene. The gas adsorption and subsequent charge transfer relieves the surface strain caused by the low coordination number of the (100) surface atoms allowing the formation of a (1 x 1) surface structure commensurate with the bulk terminated crystal structure. The surface phase change causes a transformation of the surface layer from hexagonal packing geometry to a four-fold symmetric surface which is rich in atomic defects. Lifting the hex reconstruction at room temperature resulted in a surface structure decorated with 2-3 nm Pt adatom islands with a high density of step edge sites. Annealing the surface at a modest temperature (150 C) in the presence of a high pressure of CO or H 2 increased the surface diffusion of the Pt atoms causing the adatom islands to aggregate reducing the surface concentration of low coordination defect sites. Ethylene hydrogenation was studied on the Pt(100) surface using HP-STM. At low pressure, the lifting of the hex reconstruction was observed in the STM images. Increasing the ethylene pressure to 1 Torr, was found to regenerate the hexagonally symmetric reconstructed phase. At room temperature ethylene undergoes a structural rearrangement to form ethylidyne. Ethylidyne preferentially binds at the three-fold hollow sites, which are present on the Pt(100) hex reconstructed phase, but not the (100)-(1x1) surface. The increase in ethylene pressure caused the adsorbate interactions to dominate the crystal morphology and imposed a surface layer structure that matched the ethylidyne binding geometry. The STM results also showed that the surface was reversibly deformed during imaging due to increases in Pt mobility at high pressure. The size dependence on the activity and surface chemistry of Rh nanoparticles was studied using AP-XPS. The activity was found to increase with particle size. The XPS spectra show that in reaction conditions the particle surface has an oxide layer which is chemically distinct from the surface structure formed by heating in oxygen alone. This surface oxide which is stabilized in the catalytically active CO oxidation conditions was found to be more prevalent on the smaller nanoparticles. The reaction-induced surface segregation behavior of bimetallic noble metal nanoparticles was observed with APXPS. Monodisperse 15 nm RhPd and PdPt nanoparticles were synthesized with well controlled Rh/Pd and Pd/Pt compositions. In-situ XPS studies showed that at 300 C in the presence of an oxidizing environment (100 mTorr NO or O 2) the surface concentration of the more easily oxidized element (Rh in RhPd and Pd in PdPt) was increased. Switching the gas environment to more reducing conditions (100 mTorr NO and 100 mTorr CO) caused the surface enrichment of the element with the lowest surface energy in its metallic state. Using in-situ characterization, the redox chemistry and the surface composition of bimetallic nanoparticle samples were monitored in reactive conditions. The particle surfaces were shown to reversibly restructure in response to the gas environment at high temperature. The oxidation behavior of the Pt(110) surface was studied using surface sensitive in-situ characterization by APXPS and STM. In the presence of 500 mTorr O 2 and temperatures between 25 and 200 °C, subsurface oxygen was detected in the surface layer. STM images show that these conditions were found to cause a roughened surface decorated with 1 nm islands. The formation of this surface oxide is a high pressure phenomenon and was not detected in 50 mTorr O 2. After forming the surface oxide at high pressure, its chemical activity was measured through the reaction with CO at low pressure while continuously monitoring the oxygen species with XPS. The subsurface oxygen was removed by CO oxidation at a comparable rate to the chemisorbed oxygen at 2 °C. Repeating the experiment at -3 °C reduced the reaction rate, but not the relative activity of the two chemical species suggesting that neither species is significantly more active for the CO oxidation reaction. These studies use molecular level surface characterization in the presence of gases to show the structural changes induced by gas adsorption at high pressure.« less

Oxide-derived copper (OD-Cu) electrodes exhibit higher activity than pristine copper during the carbon dioxide reduction reaction (CO 2RR) and higher selectivity toward ethylene. The presence of residual subsurface oxygen in OD-Cu has been proposed to be responsible for such improvements, although its stability under the reductive CO 2RR conditions remains unclear. This work sheds light on the nature and stability of subsurface oxygen. Our spectroscopic results show that oxygen is primarily concentrated in an amorphous 1–2 nm thick layer within the Cu subsurface, confirming that subsurface oxygen is stable during CO 2RR for up to 1 h at –1.15 Vmore » vs RHE. Besides, it is associated with a high density of defects in the OD-Cu structure. In conclusion, we propose that both low coordination of the amorphous OD-Cu surface and the presence of subsurface oxygen that withdraws charge from the copper sp- and d-bands might selectively enhance the binding energy of CO.« less

Density-functional theory is used to evaluate the mechanism of copper surface oxidation. Reaction pathways of O{sub 2} dissociation on the surface and oxidation of the sub-surface are found on the Cu(100), Cu(110), and Cu(111) facets. At low oxygen coverage, all three surfaces dissociate O{sub 2} spontaneously. As oxygen accumulates on the surfaces, O{sub 2} dissociation becomes more difficult. A bottleneck to further oxidation occurs when the surfaces are saturated with oxygen. The barriers for O{sub 2} dissociation on the O-saturated Cu(100)-c(2×2)-0.5 monolayer (ML) and Cu(100) missing-row structures are 0.97 eV and 0.75 eV, respectively; significantly lower than those have beenmore » reported previously. Oxidation of Cu(110)-c(6×2), the most stable (110) surface oxide, has a barrier of 0.72 eV. As the reconstructions grow from step edges, clean Cu(110) surfaces can dissociatively adsorb oxygen until the surface Cu atoms are saturated. After slight rearrangements, these surface areas form a “1 ML” oxide structure which has not been reported in the literature. The barrier for further oxidation of this “1 ML” phase is only 0.31 eV. Finally the oxidized Cu(111) surface has a relatively low reaction energy barrier for O{sub 2} dissociation, even at high oxygen coverage, and allows for facile oxidation of the subsurface by fast O diffusion through the surface oxide. The kinetic mechanisms found provide a qualitative explanation of the observed oxidation of the low-index Cu surfaces.« less

This work was undertaken to elucidate the facet-dependent activity of Ag for the electrochemical reduction of CO 2 to CO. To this end, CO2 reduction was investigated over Ag thin films with (111), (100), and (110) orientations prepared via epitaxial growth on single-crystal Si wafers with the same crystallographic orientations. Thus, this preparation technique yielded larger area electrodes than can be achieved using single-crystals, which enabled the electrocatalytic activity of the corresponding Ag surfaces to be quantified in the Tafel regime. The Ag(110) thin films exhibited higher CO evolution activity compared to the Ag(111) and Ag(100) thin films, consistent withmore » previous single-crystal studies. Density functional theory calculations suggest that CO 2 reduction to CO is strongly facet-dependent, and that steps are more active than highly coordinated terraces. This is the result of both a higher binding energy of the key intermediate COOH as well as an enhanced double-layer electric field stabilization over undercoordinated surface atoms located at step edge defects. As a consequence, step edge defects likely dominate the CO 2 reduction activity observed over the Ag(111) and Ag(100) thin films. The higher activity observed over the Ag(110) thin film is then related to the larger density of undercoordinated sites compared to the Ag(111) and Ag(100) thin films. Our conclusion that undercoordinated sites dominate the CO 2 reduction activity observed over close-packed surfaces highlights the need to consider the contribution of such defects in studies of single-crystal electrodes.« less